Ruthenocenoporphyrinoids─π-Conjugation Transmitted across 1,3-Substituted Ruthenocene.

Area of Science:

• Organometallic Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Ruthenocenoporphyrinoids are hybrid molecules with potential applications in catalysis and electronics.
• Understanding electronic communication and aromaticity in these systems is crucial for designing new materials.

Purpose of the Study:

• To synthesize novel ruthenocenoporphyrinoids by coordinating a [RuCp*]+ moiety to a 21-carba-23-selenaporphyrin macrocycle.
• To investigate the electronic communication between the ruthenocene unit and the macrocyclic platform.
• To assess the aromaticity and π-conjugation effectiveness in the resulting hybrid molecules.

Main Methods:

• Synthesis of ruthenocenoporphyrinoids.
• Spectroscopic analysis (¹H NMR) to probe magnetic properties.
• Density Functional Theory (DFT) calculations for molecular modeling.
• Evaluation of NICS 2D maps and EDDB plots to assess aromaticity and conjugation.

Main Results:

• Successful synthesis of ruthenocenoporphyrinoids featuring [RuCp*]+ coordination to the selenaporphyrin macrocycle.
• Observation of specific electronic communication between the ruthenocene and macrocycle.
• Maintenance of the macrocyclic ring current despite strong π-conjugation within the ruthenocene fragment.
• Theoretical data (NICS, EDDB) consistent with experimental magnetic properties (¹H NMR), indicating sustained aromaticity.

Conclusions:

• The developed synthetic route enables the creation of novel ruthenocenoporphyrinoids.
• These hybrid molecules exhibit significant electronic communication and maintain aromaticity.
• The findings provide insights into the structure-property relationships of ruthenocene-containing macrocycles.